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The 1:1 addition compound between N,N-dimethylaniline and hexafluorobenzene crystallizes at room temperature in a monoclinic cell. A lattice with space group I2/m and a = 6.927 (1), b = 14.833 (2), c = 7.071 (1) A, fl = 103.67 (1) ° was chosen rather than a Bravais lattice with space group C2/m. The structure was refined to R = 0.060 for 280 counter data. The structure is disordered with the N,N-dimethylaniline molecule in two different orientations. The partner molecules are stacked alternately in infinite columns, and the mean separation between the molecular planes is 3.52 A. The benzene rings of the partner molecules overlap in a way which is often found in charge-transfer complexes.